Dyestuffs of the anthraquinone series



Patented Nov. 30, 1943 UNITED STATES PATENT OFFICE DYESTUFFS OF THEANTHRAQUINoiiE SERIES Edwin C. Buxbaum, 'Swarthmore, Pa; assignor to E.I. du Pont de Nemours & Company, Wilmington, Del., a corporation ofDelaware 4 Claims.

This invention relates to the preparation of new dyestufls of theanthraquinone series and more particularly to the preparation of newdyestufis which dye wool and related fibers directly in gray shades.

With few exceptions, the acid wool dyestuffs of the anthraquinone serieswhich are at present employed in the dyeing of wool and related fibersare simple anthraquinone compounds, i. e. compounds where only a singleanthraquinone nucleus appears in the molecule. Severaldianthraquinonylamino compounds have been suggested for use on wool butwith few exceptions such dyes heretofore proposed from this class showpoor tinctorial strength, light fastness properties or undesirablechanges on chroming. Because of the poor dyeing properties generallyexhibited by the compounds of the dianthrimide series heretoforeconsidered for dyeing wool it has been assumed that the higher molecularweight trianthrimides would be of no value for this purpose; thisassumption being supported by the fact that the straight trianthrimidesuch as that disclosed in U. S. Patent 863,397 when sulfonated is of nopractical value as a wool dyestuff.

In the anthraquinone acid wool dyestufi field it has been difficult tofind dyes which dye in desirable gray shades except those which areproduced by the chroming of dyes which dye directly in other shades.While there are of course a few dyes of the anthraquinone series whichdye wool and related fibers directly from an acid or neutral bath ingray shades as stated above, in general these dyes are not of desirableshade, or they are defective in light-fastness, tinctorial properties orshow undesirable changes on chroming where such treatment is requiredfor other purposes. A great deal of research has therefore been expendedin an endeavor to find new dyestuffs of the anthraquinone series whichwill dye wool in desirable gray shades of good fastness properties.

It is therefore an object of the invention to produce new dyestuffs ofthe anthraquinone series which dye wool and related fibers directly ingray shades and which exhibit good dyeing and fastness properties, andwhich show relatively little change in shade on chroming.

I have found that contrary to the general belief, very desirabledyestufis for W001 and related fibers can be produced in thetrianthrimide (dianthraquinonylamino-anthraquinone) series fromtrianthrimides which carry one or more arylamino groups of the benzeneor naphthalene series directly attached thereto by converting them towater soluble sulfonic acids. In the dyes of this series the sulfonationtakes place readily with sulfuric acid of as low as 93% strengthand attemperatures as low as 20 0.,

although oleurn of as high as may be employed when desired. This ease ofsulfonation is apparently due to the presence in the molecule of thearyl amine groups of the benzene or naphthalene series into each ofwhich a sulfonic acid group is readily introduced. In the prior artwhere sulfonated anthrimide' compounds are suggested, the sulfonic acidgroups must be im troduced into the anthraquinone nucleus which requiresmore strenuous conditions of sulfon'ation. These new compounds may beprepared by condensing two moles of an amino-arylaminoanthraquinone withone mole" of a dihalogenanthraquinone, the condensation being effectedby I any of the known processes employed for the preparation of thetrianthriinide compounds. The invention also contemplates the condensation' of two moles of a halogen compound with a diai'nino diarylaminoanthraquinone such as 1,5'-' diarylamino-4,8-diani1irio anthr'aquinone.

'All of these compounds dye directly in gray shades ranging fromgreenish-gray to' reddishgray and on chroming show only a very smallchange in shade.

That these new diarylamino trianthrimide sulfonic acids, even when theycontain no further,

substituents, should dye in good strength and show good affinity forW001 and related fibers is surprising when it is known that the4,4'-di-1 quinone groups of the trianthriinide may also.

contain further simple monovalent substituents such as methyl, amino,nitro, hydroxy and halogen.

These new gray dyestuffs show good light fast ness and tinctorial power,and relatively little change in shade oh' chromi'ng.

' The following examples are given to illustrate the invention. Theparts used are by weight.

Erample 1 Thirty-one and four-tenths (31.4) parts of 1-aminol-anilino-anthraquinoiie are reacted with 13.9 parts of2;6-dichlord-anthiaduirione in 500 parts of naphthalene, sonar-15s ofpotassium acetate and one part of copper acetates at 210-215 C. foreight hours. The acetic acid which is formed during the course of thereaction'i's' allowed to distill 01f. When the reaction has beencompleted, the mass is allowed to cool to C. and diluted with 1000 partsof solvent naph- 140 C. and diluted with 500 parts of solvent tha andheld at 100 C. for 2 hours. It is then naphtha. It is then cooled to 50C. and filtered filtered, and the cake is washed with additional at thistemperature. The filter cake is washed solvent naphtha and finally withethyl alcohol with sufficient solvent naphtha to insure the reand hotWater. The base is dried at 100-110 5 moval of all naphthalene and thenwith alcohol, C. It corresponds to the following formula: hot water, anddried.

H The compound formed is slightly soluble in 0 most organic solventswith a blue shade. It e r 0: i=0

corresponds to the following formula:

H H o i'r Ten parts (10) of the above compound are added to a mixture of50 parts of sulfuric acid monohydrate and 50 parts of oleum over 6 aperiod of one hour. When al1 of the base has E I been added, thetemperature is raised to 60'70 ON N 0 C., and held there untilsulfonation is complete which usually takes about thirty minutes. The 2Dsulfonated base is then isolated by pouring out G into 800 parts of iceand water, filtering, washing acid free with brine and finally drying at100110 C. It dyes W001 in greenish-gray shades The above ompound iseasily sulfonated at which change very little upon chroming and e 25room temperature by dissolving it in 10% oleum hiblt good light fumingfastnessand allowing it to stir for 8 hours. The isola- Exampqe 2 tionof the sulfonated color proceeds in the usual manner. The dyestuffformed dyes wool in Thlrty-four and three-tenths parts Of greenish grayhades hange ery on "P- anthraquinone chroming and exhibits excellentfastness to light.

are reacted with 14 parts of 2:6-dichloro-anthraquinone in 500 parts ofnaphthalene in the pres- Example 4 ence of 50 parts of potassium acetateand 1 part of copper acetate at 210-215 C. for a period of Thirty-fourand three-tenths (34.3) parts of l- 8 hours. When the reaction has beencompleted, a ohy -p to u o q none the mass is allowed to cool to 100 C.and diare reacted With 14 parts of 1:5-diohloro-anthraluted with 1000parts of solvent naphtha. The quinone in 500 parts of naphthalene in thepresdiluted reaction mass is held two hours addience of parts ofpotassium acetate and 1.0 part tional at 100 C. and then allowed to coolslowly of copper acetate at a reflux temperature for 10 to 50 C., andfiltered at this temperature. The 40 hours. The finished condensation isdiluted with filter cake is washed with additional solvent naph- 1000cc. solvent naphtha and held at 100 C. for tha and finally with hotWater and dried. The 2 hours. It is then slowly cooled to roomtemcompound formed corresponds to the following perature and filtered,freed of naphthalene by formula: Washing with additional solvent naphthaand O CH: i i

on N NOCHs r HaC N N 0 o Ten (10) parts of the above base are dissolvedfinally washed with alcohol and hot water. The in a mixture of 50 partsof sulfuric acid monobase formed corresponds to the following formula:hydrate and 50 parts of 25% oleum. The sulfonation mass is heated to C.for one hour and then poured out into 800 parts of ice and water. It isfiltered ofi, Washed acid free with 60 brine and dried. The compoundformed dissolves in water with a dark blue color and dyes wool from anacid bath in neutral gray shades which change very little on chroming.It exhibits good afiinity for the fiber and has desirable fastnessproperties.

Example 3 Sixteen (16) parts of 1-amino-4-anilino-anthraquinone arecondensed with '7 parts of 1:5-

dichloro-anthraquinone in 250 parts of naphtha- Then (10) parts of theabove base are dissolved lene in the presence of 25 parts of potassiumin 100 parts of 12.5% oleum and heated to 40 C. acetate and 05 part ofcopper acetate at 210- until complete sulfonation has occurred. It is215 C. for a period of six hours. When the then isolated in the usualmanner. The, dyestufi condensation is complete, the mass is cooled todyes wool from an acid bathrin taupe shades,

which become considerably browner on chroming. It exhibits good fastnessto light, washing and fulling. I

' Example Thirty-one and four-tenths (31.4) parts of 1-amino-4-anilino-anthraquinone are reacted with 14 parts oflzfi-dichloro-anthraquinone in 500 parts of naphthalene in the presenceof 50 parts of potassium acetate and 1 part of copper acetate at 210-215C. for a period of 8 hours. The acetic acid'which is formed during thecondensation is allowed to distill off. The reaction mass is allowedto-cool'to 140 C. and is then diluted with 1000 parts of solvent naphthaand held at 140 C. for one hour. It is then cooled to 100 0., held therefor two hours and then cooled slowly to room temperature. The dilutedcondensation is filtered, the anthrimide washed with solvent naphtha,alcohol; and finally with water. Itcorresponds tov the followingformula:

The above compound sulfonateseasily in strong sulfuric acid to give awater soluble dyestuff which dyes wool from an acid bath in blue-grayshades which change slightly on chroming. It exhibits good fastnessproperties. I

If in the above example, there is employed 1-amino-5.-anilino-anthraquinone in place of 1-aminol-anilino-anthraquinone, a much redder shade of gray is produced.

Example 6 Forty-one (41) parts of 1-amino-2-bromo-4-para-toluidino-anthraquinone are reacted with 14 parts of1:6-dichloro-anthraquinone in 500 parts of naphthalene in the presenceof 50 parts of potassium acetate and one part of copper'acetate at210-215 C. for a period of eight hours. The condensation mass is dilutedwith suificient solvent naphtha to hold the naphthalene in solution andis then cooled to room temperature and filtered. It is washed withadditional solvent naphtha, alcohol and hot water. The black powderwhich is obtained corresponds to the following formula:

' One hundredilOO) parts of the above com.-

pound are dissolved in 1000 parts of 12.5% oleum and heated untilcomplete sulfonation is obtained. The acid mass is poured intosuflicient ice and water to bring the acid concentration down to 10%.The free disulfonic acid is precipitated out and is filtered off, washedacid free with brine and dried at -110" C. It dyes wool from an acidbath in fast gray shades.

Example 7 When the above compound is sulfonated in the usual manner,there is obtained a new gray wool dyestuif which has good fastnessproperties.

Example 8 If in the above example, there is substituted1-amino-4-chloro-anthraquinone in place of 1- chloro-anthraquinone, thefollowing compound is obtained: Q

NHzO

A NHz Upon sulfonation in the usual manner, this gives a new blue graydyestuff which dies wool from an acid bath in blue-gray shades which arefast to light and other usual fastness tests.

Example 9 NH O l H N-H O When sulfonated in 10% oleum at Gil- C. in

the'usual manner; there is obtained a new wool gray dyestufi which dieswool from an acid bath in gray shades of good fastness properties.

The condensation of the amino-arylaminoanthraquinone compounds with thedihalogen anthraquinones .may be efiected in any one of numerous. media,such as hexalin, ortho dichloroebenzene, Intro-benzene or other solventsin'place. of naphthaleneused in the examples. If naphthalene .is used,any one of numerous solvents can be employed for dilution in' place ofsolventnaphtha, for instance, toluene, benzene or dioxan. Temperaturesranging from -225 C. may be used depending on the solvent and length oftime condensed.

The sulfonation can be carried out at temperatures ranging from 20 C. toC. Sul-' furic acid. from 93% strength to 65% oleum can be used. Theweaker acids require the higher temperatures while the stronger oleumseffect anthrimide carries the arylamino groups in para positions on the'anthraquinone molecules relative to the anthrimide linkages and inwhich the aryl groups are monocyclic groups of the benzene series.

2. Compounds of the group consisting of 4,4" diani1ino-1,5-(l,1"di-anthraquinonylamino) anthraquinone sulfonic acid and its alkali metalsalts.

3. Compounds of the group consisting of 4,4 dianilino-2,6-(1,1"di-anthraquinonylam no) anthraquinone sulfonic acid and its alkali metalsalts. W

Compounds of. the group consisting. of 4,4"' dianilino1,4-(1,1"-anthraquinonyl-.

v amino) anthraquinone sulfonic acids and its alkali metal salts.

' EDWIN c. BUXVBAUM.

